Manufacture of new condensation products from natural resins



Patented Nov. 26, 1935 PATENT OFFICE MANUFACTURE OF NEW CONDENSATION PRODUCTS FROM NATURAL BESINS Josef. Binapfl, Krefeld-Uerdingen-on-the-Rhine,

Germany, assignor to I. G. Farbenindustrie Aktiengesellschaft, Frankfort-on-the-Main, Germany N Drawing. Application March 9, 1933, Serial v No. 660,169. In Germany March 30, 1931 21 Claims. (o1. 269-2) The present invention concerns the manufacture of new products from natural resins, possessing improved properties, consisting in causing the resins, anhydrides or esters thereof to act on phenols, substitution products or functional derivatives thereof in the presence of inorganic volatile halides. Instead of the resins the resin acids isolated from the same, such as for example, abietic acid, can likewise be employed.

With the knowledge at present at my disposal, I suggest that the reaction probably proceeds 'essentially in the manner that one phenol molecule attaches itself at the double bond present in the resin molecule with formation of an oxyaryl derivative of the respective resin acid. It appears that the carboxylic groups of the resin thus remain in general unaltered. The reaction may be illustrated by the following formula:

(Only the double bond required for the reaction is shown from the molecule of the resin acids; R represents an aromatic residue, R1 a.hydrogen atom or a substituent therefor such as an alkyl group, an aryl group or an acyl group).

Inparticular the new reaction products are distinguished from the starting materials by a much reduced iodine value and in general by a considerably raised softening point. Moreover, they do not give the Storch-Morawski color reaction, characteristicof natural resins, that is to say, the addition of acetic anhydride and concentrated sulphuric acid does not produce the blue coloration, characteristic of natural resins.

Among the natural resins and esters thereof, which are suitable for the manufacture of condensation products in accordance with the pres ent invention, the following may be specially mentioned: colophony, pine resin, B'atavian damar, gum mastic, copal, as well as esters of these resins with ethyl alcohol, dodecyl alcohol, glycol, glycerine, mannite, phenol and the like. In addition the mixed esters known under the name of alkyd resinsand containing the residue of an acid from a natural resin besides the residues of a .polyvalent alcohol and a polybasic acid are well adapted for the manufacture of the new conversion products. As examples of the said alkyd resins may be mentioned the condensation products obtainable from glycerine, polyglycols or polyglycerines, pentaerythrite, mannite, sorbite and the like by simultaneous or successive esterification with oneof the above mentioned natural resins and a polybasic acid, such as phthalic acid, trimellitic acid, succinic acid, maleic acid and the like.

As examples of suitable phenolic components 5 may be mentioned: phenol, naphthol, resorcinol, phenol derivatives, such as phenols alkylated in the nucleus, for example cresols and xylenols,

furthermore chlorophenols, bromophenols, chloro nitrophenols, nitrophenols, chloro cresols etc. as well as phenol ethers, such as anisol, phenetol, diphenyl ether, ditolyl ether, furthermore phenol esters, such as cres'ol acetate, dicresol carbonate, phenol propionate; phenol stearate, phenol oleate, phenol benzoate,xylenol phthalate etc.

Volatile inorganic halides appropriate for the purpose of this invention are for example hydrogen halides, such as hydrogen chloride, furthermore aluminiumchloride, titanium chloride, tin tetrachloride, boron fluoride etc., those halides being preferably used in a practically anhydrous condition. Instead of boron fluoride compounds of the same, for example, complex compounds with organic acids, such as formiatofluoro-boric acid, acetato-fluoro-boric acid, chloroacetato-fluoro-boric acid, lactato-fluoroboric acid, oleato-fiuoro-boric acid, stearatofluoro-boric acid, benzoato-fluoro-boric .acid, phthalato-fiuoro-boric acid, can also be empl'oyed as the'condensing agents.

When employing solvents, preferably those are used which do not undergo a chemical change under the reaction conditions, such as for example, carbon tetrachloride and carbon disulphide etc. Furthermore hydrocarbons, such as benzene, toluene, ligroin', gasoline, tetrahydronaphthaline and the like are suitable for the purpose of this invention.

The temperature during the reaction may vary according to the conditions I have obtained 40 good results with temperatures above 0 C., more particularly with temperatures ranging from about 0 to about 200 C.

The conversion products obtainable by condensing natural resins with a phenol or substitution products thereof are capable of being esterifled and etherifled due to the presence of free carboxylic acid groups and free phenolic hydroxy groups, e. g. by means of ethylene oxide or alkylr or aralkyl halides, such as ethyl chloride, butyl" chloride, amyl chloride, benzyl chloride, chloromethyl-isopropylnaphthaline, glycolchlorhydrin and the like, in the presence 'of an alkali. The carboxylic acid groups of the condensation products can be furthermore esterified by means of an alcohol, e. g. ethyl alcohol, dodecyl alcohol, glycol, glycerine, mannite, sorbite, phenol etc.

Alternatively the free phenolic hydroxylic groups of the conversion products obtainable by condensing natural resins with a phenol as described above are capable of being esterifled by means of acids, such as for example, by means of acetic anhydride or acid chlorides, such as acetyl chloride, oleic acid chloride, benzoyl chloride and the like. Furthermore the free phenolic 'hydroxyl groups of the condensation products obtainable from the esters of natural resins by means of free phenols can likewise be converted into fur- Example 1 100 parts by weight of a 25% solution of boron fluoride in technical crude cresol are introduced into a mixture of 300 partsby weight of American colophony (acid value 164, iodine value 175,-acetyl value 5, softening point 79 C.) and 150 parts by weight of benzene in the course of 1-2 hours with stirring at about 30-40 C. A dark brown, viscous mass is produced, which is then further stirred for about 14 hours at room temperature (15-18 0.). i

The resulting reaction product is then poured into cold water and the solvent is removed by means of steam A yellowish white solid brittle resin isthus obtaiiied which is boiled with water and after melting yields a clear resin (325 parts by weight), possessing the following constants:

Acid value 114 Iodine valv 43.5 Acetyl value 64.8 Softening point C.

The Storch-Morawski reaction is negative.

Example 2 When instead of a 25% solution of boron fluoride in technical crude cresol a 25% solution in phenol is employed a clear resinous condensation product possessing quite similar properties is obtained;

Acid value 11o Iodine value 51 Acetyl value 60 Softening point C. The. Storch-Morawsld reaction is negative.

Example 3 i v At a temperature of about 40 C. 60 parts b weight of acetato-fluoro-boric acidare introduced during 1-2 hours into a mixture -o f' 300 parts by weight of colophony (acid value 168, iodine value 170, softening point 69) 13 parts-by'weight of benzene and 75 parts by weight of technical crude cresol with stirring. After '20 hours the reaction product obtained is. poured into cold water and the solvent removed by means of steam. Then the reaction mass is freed from acid by washing with water. After melting a clear resin is obtained possessing the following constants:

Acid value 134 Acetyl value 68 Softening point IDS-107C. 5

Example 4 The residue consists of a yellowish mass, which 15 1 is washed several times with boiling water and after melting yields a honey yellow resin (110 parts by weight), possessing the following constants:

- 20 Acid value 144.2 Iodine value 63.6 Acetyl value 36.6 .Softening point 94 C.

It dissolves in acetic anhydride in the presence of 25 a drop of concentrated sulphuric acid with a I rose-red coloration.

Example 5 100-120 parts by weight of a. 25% solution of 30 boron fluoride in crude cresol are introduced in the course of 1-2 hours with stirring at about 40 G. into a mixture of 400 parts by'weight of the glycerine ester of colophony (acid value 15, iodine 35 value 1'10, acetyl value 8, softening point 83 C.)

and 200 parts by weight of benzene. A violet red mass, which later becomes reddish brown] is possessing the following constants:

Acid value r 16 Iodine value 48 I Acetyl value 68 50 Softening point 98 C,

The Storch-Morawski reaction is negative.

Example 6 25 parts by weight of a 25% solution of boron 55 fluoride in technical crude cresol are introduced into a mixture of 100 parts by weight of the glycerine ester of colophony (softening point 72 C.) and parts by weight of tetraline at a tem- 60 perature ,of 150 C. with stirring. After 30 minutes the Storch-Morawski reaction is negative. Then the reaction product is diluted with 200 parts of tetraline and-25 parts by'weight of calcium oxide and 20 parts by weight of fullers 65 earth are added and the mixture thus obtained stirred for about 1 hour at a temperature of about 4050 C. After filtering this mixture the solvent is removed by distillation. 105 parts by weight of a clear light brown resin are obtained, possessing 6 a softening point of 97-98 C.

' Example 7 Gaseous hydrogen chloride is passed at room temperature for about 40 hours into a stirred 75 mixture of parts by weight of the above resin ester, parts by weight of carbon tetrachloride and 36 parts by weight of phenol. A violet brown viscous mass, which later becomes dark brown is produced from which the solvent is' removed by means of steam. I v

The residue consists of a yellowish mass, which is washed with water. After melting a honey yellow resin (105 parts by weight) is obtained, possessing the following constants:

Acid value 18 Iodine value 59 Acetyl value 36 Softening point--. 90 C.

It dissolves with a pale rose-red coloration in acetic anhydride in the presence of a drop of concentrated-sulphuric acid.

Example 8 The resulting reaction product is poured into coldwater, the solvent removed by means of steam and the product washed until free from acid. After melting a yellowish brown resin parts by weight) is produced, possessing the following constants:

Acid value 25 Acetyl value 68 Softening point 136138 C.

Example 9 To a solution of 300 parts by weight of colophony glycol ester (acid value 24, acetyl value 16, softening point '73-'74" C.) in 130 parts by weight of benzene there are slowly added at room temperature 100 parts by weight of a 25% solu'-' tion of boron fluoride in cresol; an intensely violet colored reaction mass is produced, which is further stirred for about 20 hours. It is worked up in the same manner as described in Example 8 and after melting yields a clear yellow resin, possessing the following constants: Y

' Acid value 25 Acetyl value 69 Softening point 96 C.

Example 10 20% solution of boron fluoride in' technical crude cresol are introduced into the solution of this condensation product at 40-50 C. with vigorous stirring. The dark brown solution thus obtained is stirred for 14 hours. After this time the reaction product doesno more produce the Storch- Morawski color reaction. The solvent is removed by means of steam and the remaining resin freed from acid by washing with water. is melted in a nitrogen current. A clear resin is thus obtained having a softening point of 117 C.

sure.

Then the resin Example 11 75 parts by weight of a 30% solution of boron fluoride in phenetol are introduced in the course of 3 -4 hours at room temperature (15-18 c.) mm a mixture of 300 parts by weight of 5 colophony (acid value 164, iodine value 175, softening point 79 C.) 25 parts by weight of phenetol and parts by weight of benzene. A dark brown mass is produced, which is further stirred for some 1'7 hours at room temperature. The. reaction product is then decomposed by means of water, the solvent is removed by means of superheated steam and the product washed until free from acid. A straw yellow colored resinous mass is thus obtained, which after melting yields a clear amber, colored resin (330 parts by weight), possessing the following constants:

Acid value 103 Iodine value; 23 20 Ethoxy value 2.5% (calculated 2.7%)

Softening point"-.. 96-97 The Storch-Morawski reaction is negative. By esterifying with glycerine a clear resin is pro- Methoxy value 2.3% (calculated 2.45%) 35 Softening point 95-96C.

- Example 13 50 parts by weight'of tin tetrachloride are introduced with vigorous stirring at a temperature 40 of 45-60" ,C. in the course of 4 hours into a mixture 'of 300 parts by weight of colophony (acid value 164, iodine value 175, softening point 79 C.) 100 parts by weight of m-cre'sol methyl ether and 350 parts by weight of toluene. After stir- 45 ring for 30 hours, 200 parts by weight of toluene and 250 parts by weight of calcium oxide are added. Then the mixture is stirred at 40 C. still for 3-4 hours. The precipitate formed is filtered oif and the volatile solvents are removed from 50 the filtrate by distillation under diminished. pres- 322 parts by weight of a clear resin possessing the following constants are obtained:vv

Acid value 118 Iodine value 75 Softening point. E i-95C.

, The resin is easily soluble in linseed oil and white spirit on warming.

I Example 14 75 parts by weight of a 30% solution of boron fluoride in phenetol are introduced with stirring and cooling (about 18,19 C.) in the course of 4 hours into a mixture of 300 parts by weight-of 55 the glycerine ester of colophony (acid value 25, iodine value 170, acetyl value 10, softening point 81."C.), 150 parts by weight of benzene and 25 parts by weight of phenetol.

A wine red solution is gradually produced, 7 which is further stirred at room temperature for some .16 hours. The viscous reaction product, is decomposed with cold water, the solvent removed by means of steam and the residue washed until free from acid. A bright yellow resinous product 75 is obtained, which after melting yields a clear resin possessing the iollowing constants:

Acid value I Iodine value Acetyl value 15 Ethoxy value.. 1.9% (calculated 1.9%) Softening lull-101 C.

Example 15 By employing anisol instead oiphenetol a'duite similar product (308 parts by weight) is obtained, possessing the following constants:

Acid value 24.- Iodine value 31 Acetyl value 15 r 164, iodine value 175, softening point, 79 C.) and.

Methoxyl value 1.9% (calculated 2.04%)

Ezrample 16 300 parts by weight of colophony (acid value by means of superheated steam and the yellow resinous residue washed until free from acid. After melting a clear resin is obtained possessing the following constants:

Acid value 95 Iodine value 42 Softening point 95-96 C.

Example 1? 18 parts by weight oi boron fluoride are introduced at a temperature of YO- C. in the course of 6 hours ,into a mixture of 300 parts by weight of colophony (acid value 167, iodine value 130, softening point 70), 150 parts by weight of o-cresol acetate and parts by weight of benzene. After standing at room temperature for about 14 hours the viscous, brown reaction product is diluted with 200 parts by weight of benzene and 34 parts by weight of sodium carbonate are incorporated. The precipitate formed isv filtered off and thevolatile solvents are removed from the filtrate by distillation under'diminished pressure. 331 parts, by weight of a clear resin are obtained possessing the following constants:

Acid value a; Iodine value 82 Softening point 106 Example 18 the brown reaction product is diluted with 200 parts by weight of benzene and 46 parts by weight or sodium carbonate are incorporated. After filtering of! the precipitate formed the volatile solvents are removed from the filtrate by distilla- .aocatse tion under diminished pressure. 334 parts by weight of a clear resin possessing the following constants are obtained:

Acid value.. Softening point Example 19 the following constants:

Acid value 8 Iodine value 8i Softening point 99.

It may be mentioned that new products possessing still further valuable properties may be obtained by causing aldehydes to react with the condensation products obtainable by reacting with natural resins or esters thereof on phenol esters, for example, with the condensation prodnot obtained in accordance to the Examples i7, 18 and 19 above.

This application is a continuation in part of my co-pending application Serial No. 6015344), filed March 24th, 1932.

I claim:

1. The process which comprises reacting with a material selected from. the group consisting of natural resins and esters of natural resins upon material selected'from the group consistingpf phenols, phenols allrylated in the nucleus, aliiyl ethers and esters of phenols in the'presence of material selected from the group consisting oi boron fluoride and a complex compound of boron fluoride with an organic acid.

2. The process which comprises reacting with a material selected iro'm the group consisting of natural resins and esters oi natural resins upon material selected from the group consisting of phenols, phenols alkylated in the nucleus, alhyl ethers and esters of phenols in the presence of boron fluoride. y

3. The process which comprises reacting with a natural resin upon a phenol in the presence of boron fluoride.

'4. The process which comprises reacting with a natural resin upon a phenol in the presence of boron fluoride and a solvent.

5. The process which corriprises reacting with oolophony upon cresol in the presence of boron fluoride and benzene as a solvent at a. temperature of about 30-40 C.

6. A resinous product obtainable by reacting with a material selected from the group conslst ing'oi. natural resins and esters of natural resins upon a material selected from the group consisting of phenols, phenols alkylated in the nucleus, alkyl ethers and esters of phenols in the presence of material selected from the group consisting oi boron fluoride and a complex compound of boron fluoride with an organic acid, the reaction product being distinguished from the starting materials by a much reduced iodine value and by the non-appearance oi the blue color reaction on the addition ,of acetic anhydride and concentrated sulfuric acid, this reaction being known as the Storch-Morawski color reaction characteristic of I natural-resins.

7. A resinous reaction product obtainable by reacting with a material selected from the group consisting of natural resins and esters of natural resins upon material selected from the group consisting of phenols, phenols alkylated in the nucleus, alkyl ethers and esters of phenols in the presence of boron fluoride and a solvent, this reaction product being distinguished from the starting materials by a much reduced iodine from the starting materials by a much reduced iodine value and by the non-appearance of the blue color reaction on the addition of acetic anhydrideand concentrated sulfuric acid, this reaction being known as the Storch-Morawski color reaction, characteristic of natural resins.

9. A resinous reaction product obtainable by reacting with a natural-resin upon a phenol in the presence of boron fluoride and a solvent, this reaction product being distinguished from the starting materials by a much reduced iodine value and by the non-appearance of the blue color reaction on the addition of acetic anhydride and concentrated sulfuric acid, this reaction being known as the Storch-Morawski color reaction, characteristic of natural resins.

10. A resinous reaction product obtainable by reacting with colophony upon cresol 'in the presence" of boron fluoride and benzene as a solvent at a temperature of about 30-40 C. a

11. The process which comprises reacting with an ester of a natural resin upon a phenol in the presence of boron fluoride.

12. The process which comprises reacting with an ester of a natural resin upon a phenol in the 'presence of boron fluoride and a solvent.

' phenol in the presence of boron fluoride and a so1vent, this reaction product being distinguished from the starting materials by a. much reduced iodine value and by the non-appearance of the blue color reaction on the addition of acetic arrhydride and concentrated sulfuric acid, thisreaction being known as the Storch-Morawski color reaction, characteristic of natural resins.

15. A resinous reaction product obtainable by reacting with colophony glycerine'ester upon cresol in the presence of boron fluoride and benzene 5 as a solvent at a temperature of about 40 0., this reaction product having an iodine value of 48, a

softening point of 98 and being furthermore distinguished from the starting materials by the non-appearance of the blue color reaction at the addition of acetic anhydride and concentrated sulfonic acid, this reaction being known as the Storch-Morawski color reaction, characteristic of natural resins.

16. The-process which comprises reacting with 15 an ester of a natural resin upon an ether of a phenol in the presence of boron fluoride.

1'7. The process which comprises reacting with an ester of a natural resin upon an ether of 'a phenol inthe presence of boron fluoride and ago solvent.

18. .The process which comprises reacting with the glycerine ester of colophony upon phenetol in the presence of boron fluoride and benzene as a solvent at a temperature of about 18-19 C.

19. A resinous reaction product obtainable by reacting with an ester of a natural resin upon an ether of a phenol in the presence of boron fluoride, being distinguished from the starting materials by a much reduced iodine value and by so the non-appearance of the blue color reaction on the addition of acetic anhydride and concentrated sulfuric acid, this reaction being known as the Storch-Morawski color reaction, characteristic of natural resins.

20. A resinous reaction product obtainable by reacting with an ester of a natural resin upon an ether of a phenol in the presence of boron fluoride and a solvent, this reaction product being distinguished from the starting materials by a 40 much reduced iodine value and by the non-appcarance of the blue color reaction .on the addition of acetic anhydride and concentrated sulfuric acid, this reaction being known as the Storch-Morawski color reaction, characteristic of 5 I natural resins. o 21. A resinous reaction product obtainable by reacting with the glycerlne ester of colophony upon phenetol in the presence of boron fluoride and benzene as a solvent at a temperature of about 18-19 0., this resinous product having an iodine value of 31, a methoxyl value of 1.9, and being distinguished from the starting materials by the non-appearance of the blue color reaction at the addition of acetic anhydride and concentrated sulfuric. acid, this reaction being known as the Storch-Morawski color reaction, characteristic of natural- I 

